JPH0611908B2 - Corrosion resistant coated composite material and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a corrosion resistant coated composite material and a method for producing the same.

[Prior Art and Problems] A valve metal-iron group metal amorphous alloy based on Ni-Ta is highly corrosive, such as boiling concentrated hydrochloric acid or boiling concentrated nitric acid, in which corrosion progresses in general corrosion resistant metal materials. It is disclosed in JP-A-61-210143 that it has relatively good corrosion resistance even in an environment.

However, since the above-mentioned amorphous alloy is usually produced by the liquid quenching method, it is possible to use thin ribbons, thin wires,
Since it is restricted by the shape of powder or the like, it is not always satisfactory as a corrosion resistant material that can be used in various shapes.

On the other hand, usually, a metal having excellent corrosion resistance is used as a base material again in the film formation, but if a slight pinhole exists in the film itself or a minute crack is generated, the pinhole or the like is generated. Corrosion progresses through, especially undermining phenomenon in which corrosion rapidly progresses at the interface between the substrate and the film. In the magnetron sputtering method or the like that is generally adopted for film formation, considering the corrosion resistance, the structure of the interface is not appropriate, and it is difficult to manufacture a composite material having excellent corrosion resistance.

From the above problems, there is a demand for more efficient film formation, ensuring high-quality film quality, and forming an interface between a base material and a film having excellent corrosion resistance.

The present invention has been made in order to solve the above conventional problems, a corrosion-resistant coating composite material coated with a nitrogen-containing (iron group metal-valve metal) amorphous alloy film having excellent corrosion resistance under a harsh environment, Another object of the present invention is to provide a method for producing a corrosion-resistant coated composite material capable of efficiently forming the nitrogen-containing (iron group metal-valve metal) amorphous alloy film.

[Means for Solving the Problems] The corrosion-resistant coated composite material according to the present invention comprises a surface of a metal substrate coated with a nitrogen-containing (iron group metal-valve metal) amorphous alloy film.

The metal base material may be any metal as long as it is a corrosion resistant metal, and for example, a Ni-base alloy, a Ti-base alloy, SUS or the like can be used.

Examples of the iron group metal include Fe, Ni, Co and the like.

Examples of the valve metal include Ta, Ti, Zr,
Nb and the like can be mentioned, and it is particularly preferable to use Ta alone or Ta and Ti, Zr, and Nb in combination. In this case, it is desirable that the content of Ta be 30 at% or more.

The corrosion-resistant coated composite material according to the present invention is manufactured by the following method.

． One or more iron group metals and one or more valve metals are vapor-deposited in a nitrogen atmosphere on the surface of a metal substrate to coat a nitrogen-containing (iron group metal-valve metal) amorphous alloy film to produce a corrosion-resistant coated composite material. To do.

． Evaporate one or more iron group metals and one or more valve metals on the surface of the metal substrate, and at the same time coat the nitrogen-containing (iron group metal-valve metal) amorphous alloy film by the ion beam mixing method in which nitrogen ion irradiation is performed. , Producing a corrosion resistant coated composite material.

Another corrosion-resistant coating composite material according to the present invention is a surface coating of a metal base material having a metal phase of at least one of an iron group metal and a valve metal formed thereon and a nitrogen-containing (iron group metal-valve metal) amorphous alloy film coated thereon. It will be done.

Another corrosion resistant coated composite material according to the present invention is manufactured by the following method.

． At least one of an iron group metal and a valve metal is ion-implanted into the surface layer of the metal base material to form a metal phase, and then one or more iron group metal and one or more valve metal are placed on the surface of the base material in a nitrogen atmosphere. To deposit a nitrogen-containing (iron group metal-valve metal) amorphous alloy film on the substrate to produce a corrosion-resistant coated composite material.

． At least one of an iron group metal and a valve metal is ion-implanted into the surface layer of the metal substrate to form a metal phase, and then one or more iron group metals and one or more valve metals are deposited on the surface of the substrate. At the same time, a nitrogen-containing (iron group metal-valve metal) amorphous alloy film is coated by an ion beam mixing method in which nitrogen ion irradiation is performed to produce a corrosion-resistant coated composite material.

In the above methods (1) to (3), as the vapor deposition means of the iron group metal and the valve metal, for example, an electron beam vapor deposition method, an ion beam sputter vapor deposition method using a target of the iron group metal or the valve metal can be adopted. In the case of the sputter deposition method, an Ar ion beam is usually used. However, although the sputtering rate is low due to the formation of the nitrogen-containing (iron group metal-valve metal) amorphous alloy film,
Using a nitrogen ion beam is also a good idea under some conditions.

[Operation] According to the present invention, by coating the surface of a metal base material with a nitrogen-containing (iron group metal-valve metal) amorphous alloy film, the denseness and high corrosion resistance of the amorphous alloy film can be used in a harsh environment. A composite material having excellent corrosion resistance can be obtained.

Further, by depositing at least one iron group metal and at least one valve metal on the surface of the metal substrate in a nitrogen atmosphere, a nitrogen-containing (iron group metal-valve metal) amorphous having excellent compactness and high corrosion resistance is obtained. The alloy film can be efficiently formed on the base material, and thus a composite material having excellent corrosion resistance in a harsh environment can be manufactured.

Further, by depositing one or more iron group metals and one or more valve metals on the surface of the metal substrate and forming a film by an ion beam mixing method in which nitrogen ion irradiation is performed at the same time, the acceleration voltage, the current of the ion beam, By changing the irradiation angle etc., the sputter rate of the formed film can be controlled and the degree of mixing can be easily controlled.
It is possible to achieve densification of a film for enhancing corrosion resistance, formation of an optimum interfacial structure, improvement of adhesion to a substrate, and the like. Moreover, a nitrogen-containing (iron group metal-valve metal) amorphous alloy film can be efficiently formed by forming a film using a nitrogen ion beam as the ion beam. That is, it is possible to form an amorphous alloy film (iron group metal-valve metal) by using Ar ions as the ion beam. However, in such a method, the formed film is sputtered by the Ar ion beam and the film forming rate is relatively reduced. On the other hand, when the nitrogen ion beam is used, the amount of the formed film desorbed from the surface of the base material by ion sputtering can be reduced as compared with the case where Ar ions are used, and the film formation speed can be correspondingly increased. Further, since the amorphous state is promoted by the nitrogen content, it is not necessary to consider the residual of Ar in the film unlike the irradiation of Ar ion beam, and the nitrogen-containing (iron group metal-valve metal) amorphous alloy film can be easily formed. Can be formed.

On the other hand, Ni, which is a corrosion-resistant metal, is used as the base material of the composite material.
A base alloy, a Ti base alloy, a SUS material, etc. are used. When the base material made of these materials does not contain the composition components compositionally forming a film, or when the content is small, form a metal phase of at least one of an iron group metal and a valve metal on the surface layer of the base material. By this, the continuity of the components of the base material and the nitrogen-containing (iron group metal-valve metal) amorphous alloy film can be obtained, the adhesion of the amorphous alloy film to the base material can be improved, and the corrosion resistance at the interface between them can be improved. Can be improved.
As a result, a very small amount of pinholes and minute cracks are generated in the amorphous alloy film, and even under conditions where there is concern about the progress of the pitting reaction, the interfacial structure is modified by the metal phase formed in the surface layer. Therefore, a composite material having excellent corrosion resistance can be obtained.

The metal phase is formed on the surface layer of the base material by an ion implantation method of at least one of an iron group metal and a valve metal. In such an ion implantation method, the concentration, distribution, etc. of the metal phase can be arbitrarily controlled, and a gradient structure of the metal phase in the depth direction can be formed. The metal layer phase formed on the surface layer of the base material is preferably an amorphous phase, but even if it is crystalline, the effect is large and nitrogen may be contained. Therefore, after the ion implantation of at least one of the iron group metal and the valve metal, the nitrogen-containing (iron group metal-containing (Valve metal) By forming an amorphous alloy film, a very small amount of pinholes, minute cracks, etc. were formed in the amorphous alloy film, and it was formed on the surface layer even under conditions where there is a concern that the pitting reaction will proceed. By modifying the interfacial structure with the metal phase, it is possible to manufacture a composite material having excellent corrosion resistance. In particular, by combining the ion implantation of at least one of the iron group metal and the valve metal and the formation of the nitrogen-containing (iron group metal-valve metal) amorphous alloy film by the ion mixing method, the adhesion is excellent and the composite having the better corrosion resistance The material can be obtained.

[Examples] Examples of the present invention will be described in detail below.

Examples 1 to 3 First, pure iron (SPH) having a size of 30 × 30 × 2 mm as a base material is used.
C) A plate was prepared, one surface of which was mirror-polished, ultrasonically cleaned, dried, and then placed on a holder in a vacuum chamber equipped with ion irradiation and vapor deposition functions. Then, after evacuating the chamber to 5 × 10 ^-6 torr, Ar ions from the ion source were irradiated on the mirror surface of the pure iron plate for 5 minutes at an acceleration voltage of 5 kV for pretreatment for surface cleaning. gave.

Next, triple hearth electron beam evaporation method is used for N
i, Ta and Nb metals are Ni-40at% Ta, Ni-40
At the same time as vapor-depositing the composition of at% Nb and Ni-20 at% Nb-20 at% Ta respectively, at the same time, nitrogen ions are extracted from the ion source, accelerating voltage 20 kV, ion current 16 mA.
By performing ion beam mixing by irradiating ions under the conditions described above, three kinds of alloy films each having a thickness of 3 μm were formed on each pure iron plate to manufacture a composite material.

Example 4 After pretreating a pure iron plate in the same manner as in Example 1, 1 × 10 ⁻⁴ torr
In the nitrogen atmosphere, the Ni and Ta metals were vapor-deposited by the double-hearth electron beam evaporation method to form a Ni-40 at% Ta alloy film containing nitrogen with a thickness of 3 μm on a pure iron plate to manufacture a composite material.

Comparative Example 1 After pretreating a pure iron plate in the same manner as in Example 1, simultaneously depositing Ni and Ta metals by the electron beam evaporation method of the double hearth method onto Ar ions from the ion source and accelerating voltage 20 kV and ion current. A composite material was manufactured by irradiating ions under a condition of 16 mA to form a Ni-40 at% Ta alloy film having a thickness of 3 μm on a pure iron plate.

Comparative Example 2 After pretreating a pure iron plate in the same manner as in Example 1, the pure iron plate on the holder was heated to 750 ° C. and at the same time the Ni and Ta metals were vapor-deposited by the double-hearth electron beam evaporation method. , Nitrogen ions are extracted from the ion source and the acceleration voltage is 20k.
A composite material was manufactured by irradiating ions under the conditions of V and an ion current of 16 mA to form a Ni-40 at% Ta alloy film having a thickness of 3 μm on a pure iron plate.

When the crystallinity of the alloy films of Examples 1 to 4 and Comparative Examples 1 and 2 was determined by X-ray diffraction or the like, the alloy films of Examples 1 to 4 and Comparative Example 1 were all amorphous, It was confirmed that the alloy film of Comparative Example 2 was crystalline.

Further, a ferroxil test (pinhole test JIS H8663 porosity test; spot rate cm ⁻² ) was performed on the composite materials of Examples 1 to 4 and Comparative Examples 1 and 2.

The results are shown in Table 1 below.

Examples 5 to 20 A base material of a corrosion-resistant alloy (SUS304L, Ti alloy, Hastelloy) having a size of 30 × 30 × 2 mm, which has been subjected to the same pretreatment as in Example 1, and having a thickness of 3 μm under the conditions shown in Table 2 below. 16 kinds of composite materials were manufactured by forming an amorphous alloy film. In addition, the sputter deposition under the deposition conditions ^{* 1 in} Table 2 above was accelerated by 3k.
The target was irradiated with Ar ions of V and an ion current of 1.5 A. In addition, the composition of components in Table 2
^{* 2} : Ta-20at% Zr-10at% Ni-5at% Fe- (N), composition
^{* 3} is Ta-25at% Ti-5at% Ni-5at% Fe- (N), composition ^*
4 is Ta-10at% Nb-5at% Ti-5at% Zr-10at% Ni-5at% Co-
(N),

Comparative Example 3 The size of 30 × 30 × 2 mm, which was subjected to the same pretreatment as in Example 1,
Double hearth type electron beam deposition on SUS304L plate for N
i and Ta are vapor-deposited to have a composition of Ta-40 at% Ni, and at the same time, an Ar ion beam is extracted from the ion source,
Irradiation was performed at an accelerating voltage of 20 kV and an ion current of 16 mA, and ion beam mixing vapor deposition was performed to form a 3 μm thick amorphous alloy film on the SUS304L plate to manufacture a composite material.

Comparative Example 4 The size of 30 × 30 × 2 mm, which was subjected to the same pretreatment as in Example 1,
A composite material was manufactured by forming a Ni-40 at% Ta alloy film having a thickness of 3 μm on a SUS304L plate with a commercially available magnetron sputtering device. When this alloy film was subjected to X-ray and electron beam diffraction measurements, it was confirmed that it was an aggregate of extremely fine crystals.

Comparative Example 5 The same pretreatment as in Example 1 was carried out, and the dimensions were 30 × 30 × 2 mm.
A 3 μm-thick Ta-15 at% Ni alloy film was formed on a SUS304L plate by a commercially available magnetron sputtering apparatus to manufacture a composite material. When this alloy film was subjected to X-ray and electron beam diffraction measurements, it was confirmed to be a mixed phase of alloy fine crystals and an amorphous phase.

Comparative Example 6 Ta-15 at% Ni prepared by an argon arc melting method
The molten alloy having the above composition was rapidly solidified in a single roll method in an argon atmosphere to produce an alloy thin film having a thickness of 0.05 mm.
When this alloy thin film was subjected to X-ray diffraction measurement, it was confirmed to be crystalline.

Thus, the composite materials of Examples 5 to 20 and Comparative Examples 3 to 6
Boiled composite materials and alloy thin films. 8 normal nitric acid and 0.2
The corrosion test was performed by immersing in a solution of g / Cr ₆₊ .
The results are also shown in Table 2 of Examples 5 to 20,
The composite materials and alloy thin films of Comparative Examples 3 to 6 are shown in Table 3 below.

[Effects of the Invention] As described in detail above, according to the present invention, a dense nitrogen-containing (iron group metal-valve metal) amorphous alloy film is coated on a substrate with good adhesion, and even under a severe corrosive environment. It is possible to provide a highly versatile corrosion-resistant coating composite material having excellent corrosion resistance and free from shape restrictions, and a method for easily producing such a corrosion-resistant coating composite material.

Claims (6)

[Claims] 1. A corrosion-resistant coated composite material comprising a surface of a metal substrate coated with a nitrogen-containing (iron group metal-valve metal) amorphous alloy film. 2. One or more iron group metals and 1 on the surface of a metal substrate.
The method for producing a corrosion-resistant coated composite material according to claim 1, wherein at least one valve metal is vapor-deposited in a nitrogen atmosphere to coat the nitrogen-containing (iron group metal-valve metal) amorphous alloy film. 3. One or more iron group metals and 1 on the surface of a metal substrate.
The corrosion resistant coating composite material according to claim 1, wherein the nitrogen-containing (iron group metal-valve metal) amorphous alloy film is coated by an ion beam mixing method in which at least one valve metal is vapor-deposited and at the same time nitrogen ion irradiation is performed. Manufacturing method. 4. A corrosion-resistant coated composite material comprising a nitrogen-containing (iron group metal-valve metal) amorphous alloy film coated on the surface of a metal base material having a metal phase of at least one of an iron group metal and a valve metal formed on the surface layer. . 5. A metal phase is formed by ion-implanting at least one of an iron group metal and a valve metal into a surface layer of a metal base material, and then one or more kinds of iron group metal and one or more valves are formed on the surface of the base material. The method for producing a corrosion-resistant coated composite material according to claim 4, wherein the metal is vapor-deposited in a nitrogen atmosphere to coat the nitrogen-containing (iron group metal-valve metal) amorphous alloy film. 6. A surface of a metal base material is ion-implanted with at least one of an iron group metal and a valve metal to form a metal phase, and then one or more kinds of iron group metal and one or more kinds of valves are formed on the surface of the base material. Nitrogen-containing (iron group metal-
The method for producing a corrosion-resistant coated composite material according to claim 4, wherein the valve metal) is coated with an amorphous alloy film.